Control of insects,nematodes and acarinae with phosphonyl-carbamyloxy-phosphonates

ABSTRACT

2,2,2-TRIHALO - 1 - (O, O-DIALKYLPHOSPHONYLCARBAMOYLOXY)ETHYLPHOSPHONIC ACID ESTER ARE VERY EFFECTIVE SUBSTANCES FOR COMBATTING INSECTS, NEMATODES, MEMBERS OF THE ORDER ACARINA AND PLANT-PATHOGENIC BACTERIA AND FUNGI. THEY MAY BE APPLIED IN THE FORM OF PESTICIDAL PREPARATIONS.

United States Patent U.S. Cl. 424204 8 Claims ABSTRACT OF THE DISCLOSURE 2,2,2-trihalo 1 [0,0-dialkylphosphonylcarbamoyloxy]ethylphosphonic acid ester are very effective substances for combatting insects, nematodes, members of the order Acarina and plant-pathogenic bacteria and fungi. They may be applied in the form of pesticidal preparations.

This is a division of application Ser. No. 61,819, filed on Aug. 6, 1970, now US. Pat. No. 3,705,212.

This invention relates to phosphonic acid esters and to a process for their manufacture.

The present invention provides phosphonic acid esters of the general formula wherein R R R and R which may be the same or different, each represents an alkyl radical containing from 1 to 5 carbon atoms, X represents an oxygen or sulphur atom and Y represents a halogen atom, especially a fluorine, chlorine or bromine atom.

The phosphonic acid esters of Formula I are active against various pests of the animal and vegetable kingdom.

Those compounds in which R R R and R independently of one another denote a methyl or ethyl group, X represents an oxygen or sulphur atom and Y represents a chlorine or bromine atom, are preferred. Of these, those active substances in which R is the same as R or R is the same as R are particularly important.

The new compounds are active against all stages of development of insects and representatives of the order Acarina, for example against sucking and biting insects.

The sucking insects include, for example, Diptera and Hymenoptera, for example aphids (Aphidae) such as Myzus persicae, Doralis fabae, Rhopalosiphum padi, Macrosiphum pisi, Macrosiphum solanifolii, Cryptomyzus korschelti, Sappaphis mali, Hyalopterus arundinis, Myzus cerasi, and scale lice and woolly lice (Coccina) for example Aspidz'otus hederae, Lecanium hesperidum, Pseudococcus maritimus, varieties of Thrips (Thysanoptera), for example Hercinothrips femoralis, bugs, for example Piesma quadrata, Rhodnius prolixus, T riatoma infestans, and Cicadas, for example Euscelis bilobatus or Nephotettix bipunctatus.

Amongst the biting insects there may be mentioned, for example, Lepidoptera and Coleptera, for example Plutella macullpennis, Lymanzria dispar, Euproctis chrysorrhoea, Malocosoma neustria, Mamestra b'rassicae, Agrotis segetum, Pieris brassicae, and also Prodenia litura, Ephestia k-iihniella, Galleria mellonella, and storage pests such as Dermestes frischii, Trogoderma granarius, Tribolium castaneum, Calandra and Sitophilus zea mais, Stegobium "ice paniceum, Tenebrio molz'tor, Oryzaephilus surinamensis, Blattela germanica, Periplaneta americana, Blatta orientalis, Blaberus gigantus, Blaberus fuscus, Gryllus domesticus, Sitophilus granarius and Leptinotarsa decemlineata; varieties which live in the ground such as Agriotes sp., Melolontha melolontha; and termites such as Leucotermes reticulitermes sp. and Leucotermes flavipes.

A large number of pests is to be found under the order Acarina, for example mites and amongst these especially spider mites (Tetranychidae) such as Tetranychus telarius, T. althaeae, T. urticae, Paratetranychus pilosus, Panonychus ulmi, and gall mites (Eriophyes ribis) and Tarsonemides such as Hemz'tarsonemus latus or Tarsonemus palladus.

The order Acarina, however, also includes, for example, the ticks, that is to say ectoparasites such as Boophilus microplus, Dermanyssus gallinae, Ornithonyssus bacoti, Ornithonyssus sylviarum', Rhipicephalus bursa, Pneumonyssus caninum, Laelaps nutalli, Acarapis woodi and Psorergates ovis.

The phosphonic acid esters according to the present invention exert a strong action against insects and Acarina which are known to be pests in cultures of crop plants. For example, the rice stem borer, Chilo suppressalis, is completely destroyed by an amount of active substance of 0.02%.

Apart from the insecticidal and acaricidal action, the active substances of Formula I are also active against plant-pathogenic bacteria and fungi, and against plantpathogenic nematodes, of which the following orders may, for example, be mentioned:

Aphelenchoides, for example A phelenchus ritzemabosi, Aphelenchus fragariae, Aphelenchus oryzae, Ditylenchoides, for example Ditylenchus dipsaci, Meloidogyne, for example Meloidogyne areanaria, Meloidogyne incognz'ta, cyst-forming nematodes (Heterodera), for example Heteroclera rostochiensis, Heterodera schachtii, and root nematodes such as Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Rhadopholus.

A further very important advantage of the compounds of the present invention resides in the low toxicity to warm-blooded animals, which in part i over 600 mg. of active substance/kg. of body weight (toxicity to rats, LD measured by oral administration).

The present invention also provides a pesticidal preparation comprising as the active ingredient at least one phosphonic acid ester of the general .formula i\ X (I) wherein R R R R X and Y have the meanings given above in combination with one or more solvents, diluents, dispersing agents, adhesives or binders or a mixture of two or more of these and optionally one or more other pesticides, for example insecticides, acaricides, nematocides, bactericides or fungicides.

The compounds of the present invention may be used, for example, in the form of sprays, concentrates, dusting powders, sprinkling agents, granules, fly plates or impregnated strips containing the active substance.

In order to manufacture directly sprayable solutions of the compounds of the Formula I there may be used as solvent, .for example, mineral oil fractions of high to medium boiling range, for example diesel oil or kerosene, coal tar oil and oils of vegetable or animal origin, hydrocarbons, for example alkylated naphthalenes or tetrahydronaphthalene, optionally using xylene mixtures, cyclohexanols, ketones and also chlorinated hydrocarbons, such as trichlorethane, trichlorethylene or trichlorobenzenes and tetrachlorobenzenes. Organic solvents of boiling point above 100 C. are advantageously used.

Aqueous application forms are advantageously prepared by adding water to emulsion concentrates, pastes or wettable spraying powders. As emulsifiers or dispersing agents there may be especially mentioned non-ionic products, for example condensation products of aliphatic alcohols, mercaptans, amines or carboxylic acids having a longchain hydrocarbon radical containing from about to 20 carbon atoms with ethylene oxide, for example the condensation product of octadecyl alcohol and 25 to 30 mols of ethylene oxide, that of technical oleylamine and mols of ethylene oxide or that of dodecylmercaptan and 12 mols of ethylene oxide. As anionic emulsifiers there may be mentioned, for example, the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic acid or of abietic acid or of mixtures of these acids and the sodium salt of a petroleum-sulphonic acid. As cationic dispersing agents there may be mentioned, for example, quarternary ammonium compounds, for example cetylpyridinium bromide and dihydroxyethylbenzyldodecylammonium chloride.

In order to manufacture dusting agents and sprinkling agents, talc, kaolin, bentonite, calcium carbonate, calcium phosphate, charcoal, cork powder, Wood flour or other materials of vegetable origin, for example, may be employed in conjunction with the active ingredient.

Granules may be manufactured, for example, by dissolving an active substance of Formula I in an organic solvent and applying the solution thus obtained to a granular mineral, for example attapulgite, SiO granicalcium or bentonite and then evaporating off the organic solvent.

It is also possible to use polymer granules. They may be manufactured, for example, by mixing an active substance of Formula I with polymerizable compounds, for example urea/formaldehyde, dicyandiamide/formaldehyde melamine/formaldehyde, after which a mild polymerization is carried out, which leaves the active substances unatfected, the granulation being carried out while the gel formation is still proceeding. A more advantageous method is to impregnate finished, porous polymer granules, made of, for example, urea/formaldehyde, polyacrylonitrile or polyesters having a certain surface area and a favorable predetermina'ble absorption/ desorption ratio, with the active substance, for example in the form of a solution (for example in a low-boiling solvent) and subsequently to remove the solvent. Such polymer granules may be applied in the form of micro-granules with bulk densities of preferably 300 g./litre to 600 g./litre, also by means of sprays. The spraying may be carried out over extensive areas of crop plant cultures with, for example, the aid of aircraft.

Further pesticides, fertilizers, surface-active agents or substances for increasing the specific gravity .for example B2180 may, if desired, be added to the granules.

Granules may also be obtained by compacting the carrier material with the active substance and, if present, further additives, with subsequent comminution.

The various pesticidal preparations may be provided, in the customary manner, with additives which improve the distribution, the adhesion, the rain resistance or the pentrating power. Fatty acids, resin, glue, casein and alginate may be mentioned as examples of such substances.

In general the pesticidal preparations contain from 0.01 to 95 percent, preferably 0.1 to 80 percent, by weight of the active substance. In certain special fields of use, for example in the case of applications .from aircraft, a commercially pure active substance may also be employed.

The compounds of the present invention may be combined with known insecticidal, acaricidal and/or namatocidal active substances in order to broaden the spectrum of action, and of these substances the following, for example, may be mentioned:

4 PHOSPHORIC ACID DERIVATIVES Bis-0,0-diethylphosphoric acid anhydride (TEPP) 0,0,0,0-tetrapropyldithiopyrophosphate Dimethyl (2,2,2-trichloro-1 -hydroxyethyl) phosphonate Trichlorfon) 1,2-dibromo-2,2-dichloroethyldimethylphosphate (Naled) 2,Z-dichlorovinyldimethylphosphate (Dichlorfos) Z-methoxycarbarnyl-1-methylvinyldimethylphosphate (Mevinphos) Dimethyl-l-methyl-Z-(methylcarbamoyl)vinylphosphate cis (Monocrotophos) 3 (dimethoxyphosphinyloxy) -N-methy1-N-methoxy-ciscrotonamide 3 (dimethoxypho sphinyloxy) -N,N-dimethyl-cis-crotonamide (dicrotophos) 2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylpl1osphate (phosphamidon) 0,0-diethy1-O-2-(ethylthio)-ethylthiophosphate (Demeton) 0,0-diethyl-S-2-(ethylthio)-ethylthiophosphate S-ethylthioethyl-0,0-dimethyl-dithiophosphate (Thiometon) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (Phorate) 0,0-diethy1-S-2-[ (ethylthio )ethyl] dithiophosphate (Disulfoton) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (Oxydemetonmethyl) 0,0-dimethyl-S- 1,2-dicarbethoxyethyl) dithiopho sphate (Malathion) (0,0,0,0-tetraethyl-S,S'-methylene-bis[dithiophosphate] (Ethion) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethy1-&(N-methyl-N-formylcarbamoylmethyl)- dithiophosphate (Formotion) 0,0-dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate (Dimethat) 0,0-dimethyl-S-(N-ethylcarbamoylmethyl)dithiophosphate (Ethoatmethyl) 0,0-diethyl-S- N-isopropylcarbamoylmethyl) -dithiophosphate (Prothoat) S-N- l-cyanol-methylethyl) carbamoylmethyldiethylthiolphosphate (Cyanthoat) S- (2-a cetamidoethyl) -0,0-dimethyldithiophosphate Hexamethylphosphoric acid triamide (Hempa) 0,0-dimethyl-O p-nitrophenylthiophosphate (Parathionmethyl) 0,0-diethyl-O-p-nitrophenylthiophosphate (P'arathion) O-ethyl-O-p-nitrophenylthiophosphonate (EPN) 0,0-dimethyl-O- (4-nitro-m-tolyl) thiophosphate (Fenitrothion) 0,0-dimethyl-O-(2-chloro-4-nitrophenyl)thiophosphate (Dicapthon) 0,0-dimethyl-O-p-cyanophenylthiophosphate (Cyanox) O-ethyl-O-p-cyanopheny1phenylthiophosphonate 0,0-diethyl-O-2,4-dichlorophenylthiophosphate (Dichrofenthion) 0,2,4-dichlorophenyl-O-methylisopropylamidothiophosphate O',O-dimethyl-O,2,4,5-trichlorophenylthiophosphate (Ronnel) O-ethyl-O-Z,4,5-trichlorophenylethylthiophosphonate Trichloronat) 0,0-dimethyl-O,2,S-dichloro-4-bromophenylthiophosphate (Bromophos) 0,0-diethyl-O,2,5-dichloro-4-bromophenylthiophosphate (Bromophos-ethyl) 0,0-dimethyl-0-(2,5-dichloro-4-iodophenyl)-thiophosphate (Iodofenphos) 4-tert.butyl-Z-ch1orophenyl-N-methyl-O-methylamidophosphate (Crufomat) Dimethyl-p-(methylthio)phenylphosphate 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl) thiophosphate (Fenthion) p-Chlorophenyl-2,4,S-trichlorophenylsulphone (Tetradifon) p-Chlorophenyl-2,4,S-trichlorophenylsulphide (Tetrasul) Methyl bromide p-Chlorophenyl-phenylsulphone p-Chlorobenzyl-p-chlorophenylsulphide (Chlorobenside) 4-chlorophenyl-2,4,5-trichlorophenylazosulphide 2(p-tert.-butylphenoxy-1-methylethyl-2-chlorethylsulphite 2 (p-tert.-butylphenoxy) cyclohexyl-2-propinyl-sulphite 4,4'-dichloro-N-methylbenzenesulphonanilide N- (2-fluorol 1,2,2-tetrachlorethylthio -methanesulphonilide 2-thio-1,3-dithiolo (4,5-6)quinoxaline (Thioquinox) Chloromethyl-p-chlorophenylsulphone (lauseto (sic.)

new)

l,3,6,8-tetranitrocarbazole and Prop 2 ynyl (4-t-butylphenoxy)-cyclohexylsulphite (Propargil).

The action of the phosphonic acid esters according to the present invention may be increased by synergistic agents. Sesamin, Sesamex, piperonyl-cyclonene, piperonylbutoxide, piperonal bis[2 (2 butoxyethoxy)ethyl] acetate, sulphoxides, propyl-isomer, N-(2-ethylhexyl)-5- norbornene 2,3 dicarboxamide, octachlorodipropylether, 2-nitrophenyl-propargyl-ether, 4-chloro 2 nitrophenylpropargyl-ether and 2,4,5 trichlorophenyl-propargyl-ether are, for example, suitable for this purpose.

The present invention also provides a process for the manufacture of a phosphonic acid ester of the General Formula I which comprises reacting a phosphonic acid ester of formula i"-CHC(Y) R ()11 (II) with an 0,0-dialkylphosphonyl-isocyanate of formula \PNCO 3.0 1"; (1

wherein, in the Formulae II and III, R R R R Y and X have the meaning given above.

The reaction of (II) and (III) is preferably carried out in a solvent which is free of hydroxyl groups, for example in benzene, toluene, dioxan or methyl-ethylketone.

The following examples illustrate the invention:

EXAMPLE 1 Manufacture of [Active substance No. 1] Toxicity to rats, when administered orally: LD50=650 mg. of active substance/kg. body weight.

g. of 0,0-dimethylthiophosphonyl-isocyanate were added dropwise, with stirring, to a mixture of 38.5 g. of 2,2,2 trichloro 1 hydroxyethylphosphonic acid dimethyl ester and 150 ml. of benzene. The reaction mixture was then stirred for 5 hours at 60 C. After cooling, the reaction mixture was filtered and the solvent was distilled from the filtrate. The crude product was recrystallized from benzene-hexane. Yield: 57.6 g. Melting point: 120 C.

Analysis.-Calculated for C H Cl NO P S (percent): P, 14.6; N, 3.3. Found (percent): P, 14.3; N, 3.3.

Following the same method, 33.9 g. of 2,2,2-trichlorel-hydroxyethylphosphonic acid dimethyl ester and 23.3

10 of diethylphosphonyl-isocyanate yielded the compound of the formula (CHaO)zP-CHO C13 0 NHII (OOZHE):

[Active substance No. 2] Toxicity to rats, when administereded orally LD50=215 mg. of active substance/kg. body weight as a. very viscous dark liquid which could not be distilled.

Analysis.--Calculated for C H Cl NO P (percent): P, 14.2; N, 3.2; Cl, 24.4. Found (percent): P, 14.3; N, 3.2; CI, 23.9.

The following esters can be manufactured in a similar manner to that described above:

Active substance number R1=R2 Ra=R4 Y X Property CH3 C1 0 Dark viscous oil. 02135 01 S Oil. i-CaH; Cl 0 Viscous oil.

EXAMPLE 2 Dusting agents Equal parts of an active substance according to the invention and of precipitated silica are finely ground. Dusting agents, preferably containing l6% of active substance, can be manufactured therefrom by mixing with kaolin or talc.

Spraying powders In order to manufacture a spraying powder, the following components are mixed and finely ground:

50 parts of active substance according to the present invention 20 parts of Hisill (highly adsorbent silica) 25 parts of Bolus alba (kaolin) 3.5 parts of a reaction product of p-tert.-octylphenol and ethylene oxide and 1.5 parts of sodium l-benzyl-2-stearyl-benzimidazole-6,3'-

disulphonate.

Emulsion concentrate Easily soluble active substances can also be formulated as an emulsion concentrate in accordance with the following instruction:

20 parts of active substance,

70 parts of xylene, and

10 parts of a mixture of a reaction product of an alkyl phenoyl with ethylene oxide and calcium dodecylbenzenesulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion results.

Granules (a) 7.5 g. of one of the active substances of Formula I are dissolved in ml. of acetone and the acetone solution thus obtained is added to 92 g. of granular attapulgite (mesh size 24/ 48 meshes/ inch) The whole is well mixed and the solvent is stripped off in a rotary evaporator. Granules containing 7.5% of active substance are obtained.

(b) To manufacture 10% strength polymer granules, 1050 to 1100 g. of technical active substance of the Formula I are dissolved in 2 litres of trichlorethylene and sprayed in a fluidized bed granulator at 1.5 atmospheres gauge spraying pressure, onto 9230' g. of initially introduced porous urea/HCHO granules. The solvent can be removed again by heating the fluidizing air to approx. 50 C.

(c) To manufacture 7.5% strength weighted granules, 770 g. of a solid technical active substance of the Formula I, 500 g. BaSO 1000 g. of urea and 7730 g. of powdered,

porous polyacrylonitrile are pressed on a roll mill and subsequently crushed to the desired particle size.

EXAMPLE 3 Contact action on Musca domestica (L.) and Ceratitl's capitata 1 half each of a series of Petri dishes were each treated with 1 ml. of an acetone solution of one of substances No. 1 and No. 2 containing 1000, 100, 10.5, 2.5 and 1.25 p.p.m. of the active substance. After evaporation of the solvent, 10 supercooled house flies were introduced into each of the prepared Petri dishes, and the lid halves were put into place. After increasing time intervals, the mortality was checked at the various concentrations. The following mortality in percent was achieved after 4 hours:

Musca donestim Cemtitis capitata Action against Prodenia litura larvae 5 larvae at a time, in the L-2 stage are placed on a leaf of Malva silverstris which has previously been dipped into an aqueous solution of an active substance and thereafter been placed in a covered Petri dish, with the atmospheric moisture in the dish being maintained by a moistened cottonwool pad. In this contact and ingestion test, the action is tested after 1 day.

The following result was obtained:

Concentration Percent .p.m.] mortality Compound number:

EXAMPLE (a) The test with Ephilachna varivestis, the Mexican bean beetle, was carried out as follows: 4-5 seedlings of Phaseolus vulgaris, in the primary leaf stage, grown in a flower pot, were dipped into emulsions of the experimental preparations and subsequently allowed to dry. The test animals, L-4 stages of the beetle, were introduced into a cellophane bag, which was subsequently fixed over the treated plant by means of a rubber band. After 5 days the action of the treatment is determined by counting the live and dead animals and by calculating the percentage mortality.

With Compound No. l, the following result was achieved:

Concentration [ppm]: 1 Mortality, percent active substance No. 1 and No. 2 the following mortality was achieved after 2 days:

Concentration Mortality,

What is claimed is:

1. A method for controlling pests selected from the group consisting of insects, nematodes and acarinae which comprises applying to said pests a pesticidally effective amount of a compound of the formula P-CHO--(Y)s OR; C") dc-NH-P wherein each of R R R and R represents alkyl of from 1 to 5 carbon atoms, X represents oxygen or sulfur, and Y represents halogen.

2. The method according to claim 1 in which, in the compound, Y represents fluorine, chlorine or bromine.

3. The method according to claim 2 in which, in the compound, each of R R R and R represents methyl or ethyl, and Y represents fluorine or bromine.

4. The method according to claim 3 in which, in the compound, R is the same as R and R is the same as R 5. The method according to claim 4 in which the compound is 6. The method according to claim 4. in which the compound is wherein each of R R R and R represents alkyl of from 1 to 5 carbon atoms, X represents oxygen or sulfur, and Y represents halogen and (2) a suitable carrier.

8. The composition according to claim 7 in which R; is the same as R and R is the same as R; and each of R R R and R represents methyl or ethyl, and Y represents chlorine or bromine.

References Cited UNITED STATES PATENTS 3,365,530 1/1968 Bahr et a1. 260-938 ALBERT T. MEYERS, Primary Examiner V. D. TURNER, Assistant Examiner U.S. Cl. X.R. 260926 

